CN102686638A

CN102686638A - Alkyd dispersion, and a process for producing the same

Info

Publication number: CN102686638A
Application number: CN2010800594512A
Authority: CN
Inventors: T.J.扬; G.E.斯皮尔曼; S.萨布拉莫尼安; R.E.德拉姆莱特; D.D.玛尔; R.P.劳尔; A.格雷森; R.桑多瓦尔; A.玛德考尔
Original assignee: Dow Global Technologies LLC; Rohm and Haas Co
Current assignee: Dow Global Technologies LLC; Rohm and Haas Co
Priority date: 2009-10-30
Filing date: 2010-11-01
Publication date: 2012-09-19
Anticipated expiration: 2030-11-01
Also published as: EP2493955A1; US8709607B2; US20120244288A1; US9200177B2; WO2011053904A4; WO2011053904A1; US20110207850A1; CN102686638B

Abstract

The instant invention provides a high-solid, solvent-free alkyd dispersion, and a continuous process for producing the same. The aqueous alkyd dispersion, according to the present invention comprises (a) from 40 to 70 percent by weight of one or more alkyds based on the total weight of the dispersion, wherein each one or more alkyds has an acid value of less than 20 and a molecular weight (Mn) in the range of greater than 1000 Dalton; (b)from less than 10 percent by weight of one or more surfactants, based on the total weight of the dispersion; and (c) from 30 to 55 percent by weight of water, based on the total weight of the dispersion; and the dispersion has an average particle size diameter in the range of 0.05 to 5 [mu]m.

Description

The alkyd dispersion-s, and preparation method thereof

The cross reference of related application

The application is a non-provisional application; Require the U.S. Provisional Patent Application 61/256 that is entitled as " ALKYD DISPERION; AND A PROCESS FOR PRODUCING THE SAME " of submission on October 30th, 2009; 389 right of priority, its instruction be through with reference to incorporating the application into, below as duplicating in full.

Technical field

The present invention relates to moisture, high solid, solvent-free alkyd dispersion-s, and preparation method thereof.

Background technology

Alkyd is the main member in trade sales coating market.The major portion of this sales item is still based on solvent-based coating.It is more and more important that water-based paint becomes, because solution stands more and more stricter volatile organic compounds (" VOC ") regulation.At present, but based on the alkyd of water be emulsion or diminishing thing (water-reducibles) (can with water-soluble mixed solvent in) form.Alkyd based on water uses the low-molecular-weight resin preparation at present; This low-molecular-weight resin or have high acid value (for example for amine neutralization greater than 50; Thereby improve water-dispersible through forming salt), or have high-load emulsifying agent or stablizer or particular functional and turn into for example with polyoxyethylene glycol or contain the compound chemistry modification of sulphonate/salt.

But, still need have alkyd dispersion-s highly filled, ultralow volatile organic compounds, wherein coating performance and performance and need not functionalized resins grade solvent alkyd those coatings quite.Therefore, the present invention provides has alkyd dispersion-s highly filled, ultralow volatile organic compounds, wherein coating performance and performance and to need not those coatings of grade solvent alkyd of functionalized resins suitable.

Summary of the invention

That the present invention provides is moisture, high solid, solvent-free alkyd dispersion-s, and preparation method thereof.

In one embodiment; The present invention provides high solid, solvent-free moisture alkyd dispersion-s; Comprise: (a) one or more alkyd of 40 to 70 weight %, based on the gross weight of said dispersion-s, wherein said one or more alkyd acid number separately is less than 20 and molecular weight (M _n) greater than 1000 dalton; (b) be less than one or more stablizers of 10 weight %, based on the gross weight of said dispersion-s; (c) water of 30 to 55 weight % is based on the gross weight of said dispersion-s; The median size of wherein said dispersion-s is 0.05 to 5 μ m.

In interchangeable embodiment; The present invention also provides the continuation method of moisture, the high solid of preparation, solvent-free alkyd dispersion-s; May further comprise the steps: (1) provides one or more fusions or liquid alkyd, and wherein said one or more fusions or liquid alkyd acid number separately are less than 20 and molecular weight (M _n) greater than 1000 dalton; (2) one or more stablizers are provided; (3) water is provided; (4) one or more neutralizing agents randomly are provided; (5) in water in the presence of said one or more stablizers and optional said one or more neutralizing agents said one or more fusions of continuous emulsification or liquid alkyd; (6) thus preparation high dispersive phase emulsion; (7) other water is provided; (8) said high dispersive phase emulsion is contacted with said other water; (9) thus prepare said moisture alkyd dispersion-s; Wherein said alkyd dispersion-s comprise 40 to 70 weight % said one or more alkyd, be less than said one or more tensio-active agents of 10 weight %, and the median size of wherein said dispersion-s is 0.05 to 5 μ m.

In interchangeable embodiment, the present invention provide according in the aforementioned embodiments each moisture alkyd dispersion-s, prepare the continuation method of this dispersion-s, different is that said one or more alkyd are neutralized to many 100% by neutralizing agent.

In interchangeable embodiment, the present invention provide according in the aforementioned embodiments each moisture alkyd dispersion-s, prepare the continuation method of this dispersion-s, different is that said one or more alkyd are neutralized to many 200% by neutralizing agent.

In interchangeable embodiment, the present invention provide according in the aforementioned embodiments each moisture alkyd dispersion-s, prepare the continuation method of this dispersion-s, the viscosity of said dispersion-s that different is is 100 to 10,000cP.In interchangeable embodiment; The present invention provides the coating that is derived from the moisture alkyd dispersion-s of the present invention; With in further embodiment; The present invention provides the method that forms the coating that is derived from the moisture alkyd dispersion-s of the present invention, and this coating shows good anti-wiping (scrub resistance).

In interchangeable embodiment; The present invention provides the coating that is derived from the moisture alkyd dispersion-s of the present invention; Wherein said coating has anti-preferably wiping, the anti-tannin contaminative of improvement, and/or the anti-grain raising property of improving (grain raising resistance).

In interchangeable embodiment, the present invention provides moisture alkyd dispersion-s, and wherein said alkyd dispersion-s has the hot ageing stability of improvement.

Embodiment

That the present invention provides is moisture, high solid, solvent-free alkyd dispersion-s and prepare the continuation method of this dispersion-s.Comprise one or more alkyd of (a) 40 to 70 weight % according to moisture, high solid of the present invention, solvent-free alkyd dispersion-s, based on the gross weight of said dispersion-s, wherein said one or more alkyd acid number separately is less than 20 and molecular weight (M _n) greater than 1000 dalton; (b) be less than one or more stablizers of 10 weight %, based on the gross weight of said dispersion-s; (c) water of 30 to 55 weight % is based on the gross weight of said dispersion-s; The median size of wherein said dispersion-s is 0.05 to 5 μ m.

The alkyd dispersion-s comprises one or more alkyd of 40 to 70 weight %.The application comprises and discloses all single numerical value and subranges of 40 to 70 weight %; For example, weight percent can for lower value 40,45,50,55 or 60 to higher limit 60,65 or 70.One or more alkyd acid number separately is 20 or lower.The application comprises and discloses 20 or all single numerical value and subranges of lower acid number; For example, acid number can for lower value 0.1,0.5,1,2,5,70 or 10 to higher limit 5,7,10,15 or 20.One or more alkyd molecular weight (M separately _n) be equal to or greater than 1000 dalton; For example, be equal to or greater than 2000 dalton, or in interchangeable embodiment, be equal to or greater than 4000 dalton.

Be applicable to that Synolac of the present invention is 100 to 1,500 in the viscosity of the shearing rate of 80 ° of C and 0.10/sec, 000 centipoise (mPas).The application comprises and discloses at 100 to 1,500 of the shearing rate of 80 ° of C and 0.10/sec, all single numerical value and subranges of 000 centipoise (mPas); For example, the viscosity in the shearing rate of 80 ° of C and 0.10/sec can be lower value 100,1000,5000,15000 or 25000 centipoise (mPas) to higher limits 100,000,250,000,500; 00,750,000,1,000; 000 or 1,500,000 centipoise (mPas).

Synolac is that polyvalent alcohol and poly carboxylic acid and various siccative oil and semi-drying oil are in varing proportions through chemically combined polyester.Polyvalent alcohol can include but not limited to, for example following component: terepthaloyl moietie, glycol ether, NSC 6366,1,4-butyleneglycol, 1,6-pinakon, glycerine, tetramethylolmethane, Sorbitol Powder and N.F,USP MANNITOL.

Therefore suitable glycol comprises terepthaloyl moietie, Ucar 35, glycol ether, triglycol, Tetraglycol 99, five glycol, hexaethylene glycol, seven glycol, eight glycol, nine glycol, ten glycol, NSC 6366, glycerine (glycerol), 1, ammediol, 2,4-dimethyl--2-ethyl-hexane-1; 3-glycol, 2,2-dimethyl--1,2-Ucar 35,2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1; Ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1; 5-pentanediol, 1,6-pinakon, 2,2; 4-trimethylammonium-1,6-pinakon, thiodiethanol, 1,2-cyclohexanedimethanol, 1; 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2; 4-trimethylammonium-1,3-pentanediol, 2,2; 4-trimethylammonium-1,3-tetramethylene glycol, p-Xylol glycol, hydroxyl neo-pentyl hydroxy new pentane acid ester, decamethylene-glycol, Hydrogenated Bisphenol A 99, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, erythritol, threitol, Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, glycerine (glycerine), trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride, dimethylol propionic acid etc.

Poly carboxylic acid can include but not limited to phthalic acid, toxilic acid, fumaric acid, m-phthalic acid, succsinic acid, hexanodioic acid, nonane diacid and sebacic acid, terephthalic acid, tetrachlorophthalic tetrachlorophthalic anhydrid, Tetra Hydro Phthalic Anhydride, dodecanedioic acid, sebacic acid, nonane diacid, 1; 4-cyclohexane dicarboxylic acid, 1; 3-cyclohexane dicarboxylic acid, 2, the acid anhydrides and the ester (when it exists) thereof of 6-naphthalene dicarboxylic acids, pentanedioic acid, trimellitic anhydride, phenylformic acid, Hydrocerol A, pyromellitic acid anhydride, trimesic acid, sulfoisophthalic acid sodium and such acid.

Siccative oil can include but not limited to Oleum Cocois, fish oil, Toenol 1140, tung oil, Viscotrol C, cottonseed oil, Thistle oil, sunflower oil, VT 18 and Yatall MA.

Except the polyvalent alcohol amount that the partly-hydrolysed oil with lipid acid, fatty ester or natural generation reacts; Can use the polyvalent alcohol of other amount or molecular weight that other branching agent (like poly carboxylic acid) makes Synolac and branching to increase, and the polyvalent alcohol of said other amount or other branching agent can be selected from trimethylolethane, tetramethylolmethane, erythritol, threitol, Dipentaerythritol, Sorbitol Powder, glycerine, trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride, dimethylol propionic acid and TriMethylolPropane(TMP).

Synolac can pass through, and for example, the direct fusion of glycerine, Tetra hydro Phthalic anhydride and siccative oil prepares.Can add solvent and reduce viscosity.The poly carboxylic acid, polyvalent alcohol and the oil that use various ratios are to obtain having the Synolac of various character, as known in the art.

Alkyd may further include any or multiple modification; For example, alkyd can be polyurethane-modified, acrylic-modified, phenylethene modified, the vinyl ester modification, the vinyl ether modification, organic-silicon-modified, epoxy resin modification and combination etc.

One or more alkyd can, for example, be one or more urea alkyd (uralkyds), promptly urethane-modified alkyd.Urea alkyd can be through making alkyd and the POLYMETHYLENE POLYPHENYLISOCYANATE and optional other component reaction preparation with isocyanate-reactive group with isocyanate-reactive group.Isocyanate-reactive group be defined as with isocyanate groups (NCO) group of reaction, instance comprises-OH ,-NH ₂,-NH-and-SH.Preferred isocyanate-reactive group is-OH.Other component includes but not limited to polyamines and polyvalent alcohol, for example have can be in water the polyvalent alcohol of dispersive group, be described below.

The instance of suitable POLYMETHYLENE POLYPHENYLISOCYANATE (being generally vulcabond) comprises aliphatic series and alicyclic polyisocyanates; Ethylidene diisocyanate, 1 for example; 6-hexamethylene diisocyanate HDI, isophorone diisocyanate (IPDI), hexanaphthene-1; 4-vulcabond, 4; 4'-dicyclohexyl methane diisocyanate, cyclopentadiene vulcabond, right-four-methyl dimethoxy phenylene diisocyanate (right-TMXDI) and meta-isomer (-TMXDI), hydrogenation 2,4 toluene diisocyanate and hydrogenation 2, the 6-tolylene diisocyanate.Also can use araliphatic and aromatic polyisocyanate; For example right-XDI, 1,4-phenylene vulcabond, 2,4 toluene diisocyanate, 2; 6-tolylene diisocyanate, 4; 4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate and 1,5-naphthalene diisocyanate.Particularly preferably be 2,4 toluene diisocyanate (TDI), randomly with its 2, in the 6-mixture of isomers.

The suitable examples of polyhydric alcohols that is used to prepare urea alkyd (for example comprises two functional alcohol, trifunctional alcohol; Glycerine, TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, trihydroxy-ethyl isocyanuric acid ester etc.), tetravalent alcohol or higher alcohols (for example, tetramethylolmethane, Glycerol dimer etc.) and combination thereof.Trifunctional alcohol is preferred, is because the degree of branching that they allow.If use, two functional alcohol (or glycol) are preferably to use with trifunctional alcohol or higher alcohols combination.The instance of suitable glycol comprises NSC 6366 (NPG), terepthaloyl moietie, Ucar 35, glycol ether, triglycol, Tetraglycol 99, five glycol, hexaethylene glycol, seven glycol, eight glycol, nine glycol, ten glycol, 1, ammediol, 2,4-dimethyl--2-ethyl-hexane-1,3-glycol, 2; 2-dimethyl--1,2-Ucar 35,2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1; 3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, 2; 2,4-trimethylammonium-1,6-pinakon, thiodiethanol, 1,2-cyclohexanedimethanol, 1; 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2; 4-trimethylammonium-1,3-pentanediol, 2,2; 4-trimethylammonium-1,3-tetramethylene glycol, p-Xylol glycol, hydroxyl neo-pentyl hydroxy new pentane acid ester, decamethylene-glycol and Hydrogenated Bisphenol A 99.

The reaction mixture of preparation alkyd comprises the polymerisate and the combination thereof of one or more aliphatic series or aromatic multi-carboxy acid, its esterification.Use like the application, term " poly carboxylic acid " comprises poly carboxylic acid and acid anhydride thereof simultaneously.Be suitable for polycarboxylic instance of the present invention and comprise phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, naphthalic acid and acid anhydride thereof and and combination.

The POLYMETHYLENE POLYPHENYLISOCYANATE that also can use the mixture of POLYMETHYLENE POLYPHENYLISOCYANATE and pass through to introduce carbamate, allophanate, urea, biuret, carbodiimide, uretonimine (uretonimine) or isocyanuric acid ester residue (residues) modification.

Alkyd can be included in dispersive group in the water, for example, ionic group such as anionic carboxylic acid group, and/or non-ionic in water dispersive group such as polyethylene oxide (PEO) chain group.

The suitable polyvalent alcohol with hydroxy-acid group is, for example, lower molecular weight (500 dalton) and polyvalent alcohol, particularly glycol, after with suitable alkali neutralization, can the carboxylate anion group be provided thus by hydroxy-acid group.Suitable glycol includes but not limited to the acid of dihydroxyl alkanol and 2,2-dimethylol propionic acid (DMPA).

One or more alkyd can partially or completely neutralize with neutralizing agent.In some embodiments, the neutralization of one or more alkyd on mole foundation can be 5 to 200%; Or in interchangeable embodiment, its neutralization on mole foundation can be 25 to 100%.Neutralizing agent can be an alkali, like volatile caustic or Pottasium Hydroxide.Other neutralizing agent for example can comprise Lithium Hydroxide MonoHydrate or sodium hydroxide.In the interchangeable embodiment of another kind, neutralizing agent can, for example, be carbonate.In the interchangeable embodiment of another kind, neutralizing agent can, for example, be any amine, like monoethanolamine or 2-amino-2-methyl-1-propanol (AMP).The amine that is used for the disclosed embodiment of the application can comprise monoethanolamine, diethylolamine, trolamine and TRIS AMINO (each is available from Angus), NEUTROL TE (available from BASF) and tri-isopropanolamine, HSDB 338 and N; (each is available from The Dow Chemical Company for the N-dimethylethanolamine; Midland, MI).Other useful amine can comprise ammonia, single methylamine, n n dimetylaniline, Trimethylamine 99, mono aminoethane, diethylamine, triethylamine, single Tri N-Propyl Amine, dimethyl n propylamine, N-carbinolamine, N-amino ethyl ethanolamine, N methyldiethanol amine, monoisopropanolamine, N; N-dimethyl propanol amine, 2-amino-2-methyl-1-propanol, three (hydroxymethyl)-aminomethane, N; N, N'N'-four (2-hydroxypropyl) quadrol, 1.2-diaminopropanes.In some embodiments, can use the mixture of amine or the mixture of amine and alkali.Will be apparent to those skilled in the art that the particular composition of being prepared is depended in the selection of suitable neutralizing agent, and know that such selection is within those of ordinary skills' ken.

Moisture alkyd dispersion-s also comprises one or more stablizers that are less than 10 weight %, based on the gross weight of dispersion-s.The application comprises and discloses all single numerical value and subranges that are less than 10 weight %; For example, weight percent can for lower value 1,2,3,4,5,6 or 7 weight % to higher limit 2,3,4,6,8,9 or 10.Stablizer can, for example, be external stabilization agent or internal stability agent.In the embodiment of selecting, stablizer can be tensio-active agent, polymkeric substance or its mixture.In some embodiments, stablizer can be a polar polymer, and it comprises the polar group as comonomer or grafted monomer.In exemplary embodiment, stablizer comprises one or more polar polyolefins, and it comprises the polar group as comonomer or grafted monomer.Exemplary polymer stabilizer includes but not limited to, ethylene-acrylic acid (EAA) multipolymer and ethylene-methacrylic acid copolymer are as with trade mark PRIMACOR ^TMFrom commercial available from Dow Chemical Company, with trade mark NUCREL ^TMFrom commercial available from E.I.DuPont de Nemours with trade mark ESCOR ^TMFrom commercial available from ExxonMobil Chemical Company those, and it is described in USP 4,599, and 392,4,988,781 and 5,938,437, aforementioned each piece document is all through with reference to incorporating the application into.Other exemplary polymer stabilizer includes but not limited to, ethylene-propylene acetoacetic ester (EEA) multipolymer, ethylene-methyl methacrylate methyl esters (EMMA) multipolymer and ethylene-propylene acid butyl ester (EBA) multipolymer.Also can use other ethene-polymers of carboxylic acid.Will be apparent to those skilled in the art that and also can use a lot of other useful polymkeric substance.

Spendable other stablizer comprises but is not limited to, and comprises longer chain fatty acid, soap or the fatty acid alkyl ester of 12 to 60 carbon atoms.In other embodiments, longer chain fatty acid or soap can comprise 12 to 40 carbon atoms.

Stablizer can partially or completely neutralize with neutralizing agent.In some embodiments, the neutralization of stablizer (like longer chain fatty acid or EAA) on mole foundation can be 25 to 200%; Or in interchangeable embodiment, its neutralization on mole foundation can be 50 to 110%.For example, for EAA, neutralizing agent can be an alkali, like volatile caustic or Pottasium Hydroxide.Other neutralizing agent can comprise for example Lithium Hydroxide MonoHydrate or sodium hydroxide.In the interchangeable embodiment of another kind, neutralizing agent can, for example, be carbonate.In the interchangeable embodiment of another kind, neutralizing agent can, for example, be amine, for example monoethanolamine or 2-amino-2-methyl-1-propanol (AMP).The amine that is used for the disclosed embodiment of the application can comprise monoethanolamine, diethylolamine, trolamine and TRIS AMINO (each is available from Angus), NEUTROL TE (available from BASF) and tri-isopropanolamine, HSDB 338 and N; (each is available from The Dow Chemical Company for the N-dimethylethanolamine; Midland, MI).Other useful amine can comprise ammonia, single methylamine, n n dimetylaniline, Trimethylamine 99, mono aminoethane, diethylamine, triethylamine, single Tri N-Propyl Amine, dimethyl n propylamine, N-carbinolamine, N-amino ethyl ethanolamine, N methyldiethanol amine, monoisopropanolamine, N; N-dimethyl propanol amine, 2-amino-2-methyl-1-propanol, three (hydroxymethyl)-aminomethane, N; N, N'N'-four (2-hydroxypropyl) quadrol, 1.2-diaminopropanes.In some embodiments, can use mixture or the amine and the surfactant mixtures of amine.Will be apparent to those skilled in the art that the particular composition of being prepared is depended in the selection of suitable neutralizing agent, and know that such selection is within those of ordinary skills' ken.

The other stablizer that can be used for the present invention practice comprises but is not limited to cats product, AS or nonionogenic tenside.The instance of AS includes but not limited to sulphonate, carboxylate salt and phosphoric acid salt.The instance of cats product includes but not limited to quaternary amine.The instance of nonionogenic tenside includes but not limited to comprise the segmented copolymer and the organic silicon surfactant of oxyethane.The stablizer that is used for the present invention's practice can be external surfactants or inner surface promoting agent.External surfactants is in the dispersion-s preparation, chemical reaction not to take place to be incorporated into the tensio-active agent in the Synolac.The instance that is used for the application's external surfactants includes but not limited to dodecylbenzene sulfonate and dodecane sulfonate.The inner surface promoting agent is chemical reaction can take place be incorporated into the tensio-active agent in the Synolac in the dispersion-s preparation.The instance that is used for the application's inner surface promoting agent comprises 2,2-dimethylol propionic acid and salt thereof.Other tensio-active agent that can be used for practice of the present invention comprises cats product, AS, nonionogenic tenside or its combination.Various commercially available tensio-active agents can be used for the disclosed embodiment of the application, and this comprises: OP-100 (StNa), and OPK-1000 (potassium stearate), and OPK-181 (potassium oleate), each is available from RTD Hallstar; UNICID 350, available from Baker Petrolite; DISPONIL FES 77-IS, DISPONIL FES-32-IS, DISPONIL FES-993 and DISPONIL TA-430, each is available from Cognis; RHODAPEX CO-436, SOPROPHOR 4D384,3D-33, and 796/P, RHODACAL BX-78 and LDS-22, RHODAFAC RE-610, and RM-710 and SUPRAGIL MNS/90, each is available from Rhodia; E-sperse 100, and E-sperse 700 and E-sperse 701 are available from Ethox Chemical; With TRITON QS-15, TRITON W-30, DOWFAX 2A1, DOWFAX 3B2; DOWFAX 8390, DOWFAX C6L, TRITON X-200, TRITON XN-45S; TRITON H-55, TRITON GR-5M, TRITON BG-10 and TRITON CG-110; Each is available from The Dow Chemical Company, Midland, Michigan.

The alkyd dispersion-s also comprises fluid medium.Fluid medium can be any medium; For example, fluid medium can be a water.Alkyd dispersion-s of the present invention comprises the fluid medium of 35 to 75 weight %, based on the gross weight of dispersion-s.In specific embodiment, water-content can be 35 to 65 weight %, or is 35 to 55 weight % in interchangeable embodiment, or is 45 to 55 weight % in interchangeable embodiment, based on the gross weight of dispersion-s.Can preferably control the water-content of alkyd dispersion-s, make that solids content is that about 1 weight % is to about 90 weight %, based on the gross weight of dispersion-s.In specific embodiment, solids content can for about 10 weight % to about 70 weight %.In other specific implementations, solids content is that about 40 weight % are to about 70 weight %.In some other embodiment, solids content is that about 25 weight % are to about 55 weight %.

The median size of the solids content of alkyd dispersion-s is 0.05 to 5 μ m.The application comprises and discloses all single numerical value and subranges of 0.05 to 5 μ m; For example, median size can for lower value 0.05,0.1,0.2,0.5 or 1 μ m to higher limit 1,2,3,4 or 5 μ m.

Can be further and following component blend according to alkyd dispersion-s of the present invention: one or more binder ingredientss, for example acrylic latex, vinylacrylic acid latex, styrene acrylic latex, vinyl-acetic ester ethylene latex and combination thereof; One or more optional solvents; One or more optional solubility promoters; One or more optional fillers; One or more optional additives; One or more optional pigment, for example titanium oxide, mica, lime carbonate, silicon-dioxide, zinc oxide, milled glass, aluminum trihydrate, talcum, ANTIMONY TRIOXIDE SB 203 99.8 PCT, flying dust and clay; One or more optional dispersion agents, for example amino alcohol and polycarboxylate; One or more optional tensio-active agents; One or more optional skimmers; One or more optional sanitass, remove marine alga agent and combination thereof at biological example killing agent, mould inhibitor, mycocide; One or more optional thickening materials, for example based on the thickening material of cellulose family, the ethoxylated urethane thickening material (HEUR) of the alkali-soluble emulsion of hydroxy ethyl cellulose, hydrophobically modified and hydrophobically modified for example; One or more optional biocides; One or more optional skimmers; One or more optional flowing agents; One or more optional flow agents; Or one or more optional other neutralizing agents, for example oxyhydroxide, amine, ammonia and carbonate.

The alkyd dispersion-s can further comprise the part of tinting material as the alkyd dispersion-s.Can use multiple tinting material.Instance comprises pigment for example yellow, red-violet colour and green pigment.As black colorant, can use carbon black and use below shown in the tinting material of yellow/red-violet colour/cyan colorant furnishing black.The tinting material that the application uses comprises dyestuff, pigment and predispersion etc.These tinting materials can use separately, use or use as solid solution with form of mixtures.In various embodiments, pigment can be provided as following form: the pigment of the pigment that is untreated, processing, the pigment of beforehand research mill, pigment powder, pigment press cake, the female batch of material of pigment, recovery pigment and solid or liquid pigment predispersion.Such as the application use, the pigment that is untreated is following granules of pigments, not to its surface applied moist curing, various being coated with is deposited on its surface.The pigment of pigment and processing of being untreated further disclose in 20060078485 with U.S. Patent application at the open WO 2005/095277 of PCT to be discussed, and the relevant portion of these documents is incorporated the application into through reference.On the contrary, the pigment of processing can experience moist curing, thereby for example at particle surface coating of metal oxides is provided.The instance of coating of metal oxides comprises aluminum oxide, silicon-dioxide and zirconium white.Reclaim pigment and also can be used as initial granules of pigments, wherein reclaiming pigment is the pigment after the moist curing that quality is not enough to sell as coating pigment.

Exemplary colorant particle includes but not limited to following pigment; For example can use yellow colorants, representational compound is condensation azo cpd (condensed azo compound), Isoindolone compounds, anthraquinone compounds, azo metal complexing methylidyne compound and allyl group amide compound.As the red-violet colour tinting material; Can use condensation azo cpd, diketopyrrolo-pyrrole compound, anthraquinone, quinoline a word used for translation ketone compound, basic dye color lake (base dye lake) compound, naphthol compound, benzimidazolone compound, thioindigo compound and perylene compound.As cyan colorant, can use copper phthalocyaine dye compound and verivate thereof, anthraquinone compounds, basic dye color lake compound etc.

In one embodiment, thus for example ammonia, Pottasium Hydroxide or this both combination melt kneading form the alkyd dispersion-s with water and neutralizing agent in forcing machine with one or more alkyd, one or more stablizers.In another embodiment, thus for example ammonia, Pottasium Hydroxide or this both combination melt kneading form the alkyd dispersion-s with water and neutralizing agent in forcing machine with one or more liquid alkyd, one or more stablizers.In some embodiments, at first dispersion-s is diluted to and comprises about 1 water, further be diluted to the water that comprises greater than about 25 weight % then to about 20 weight %.

Can use any melt kneading method known in the art.In some embodiments, use for example twin screw extruder of kneader,

mixing machine, single screw extrusion machine or multiple screw extruder.Preparation is not limited especially according to the method for dispersion-s of the present invention.For example, forcing machine is for example twin screw extruder in some embodiments, with back pressure type setter, Melt Pump or toothed gear pump coupling.Exemplary embodiment also provides alkali container and initial condition container, and said both comprise pump separately.The alkali of aequum and initial condition are provided by alkali container and initial condition container respectively.Can use any suitable pump, but for example use pressure flow to be the pump of about 150cc/min in some embodiments, thereby alkali and initial water are provided to forcing machine at 240 crust.In other embodiments, the liquid infusion pump provides the flow of 300cc/min or clings to the flow that 600cc/min is provided 133 at 200 crust.In some embodiments, in preheater, preheat alkali and initial water.

One or more alkyd that are liquid, pellet, powder or sheet-form are fed to the inlet of forcing machine from feeder, wherein resin fusion or be mixed in this forcing machine.Can one or more fillers of choosing wantonly and one or more alkyd be fed in the forcing machine through feeder simultaneously; Or in interchangeable embodiment, can be earlier one or more fillers be mixed in one or more alkyd, then this mixed thing is fed in the forcing machine through feeder.In interchangeable embodiment, can further one or more other fillers be metered in the fusion mixed thing that comprises one or more alkyd and one or more fillers of choosing wantonly through the inlet before the emulsion band.In some embodiments, stablizer through and add in one or more alkyd with one or more alkyd, and in other embodiments, stablizer is fed in the twin screw extruder separately.Then with resin melt from the emulsification zone that the mixing and the transit area of forcing machine is delivered to forcing machine, add water and alkali at emulsification zone passage inlet from the original bulk of water and alkali container.In some embodiments, can in these current, add stablizer extraly or exclusively.In some embodiments, can add from the dilution of forcing machine and the other dilution water of the water receptacle in the cooled region through water inlet.Usually, dispersion-s is diluted at least 30 weight % of the water in the cooled region.And, can the mixture diluted of dilution is any inferior, until reaching required dilution level.In some embodiments,, water is not added in the twin screw extruder, but add in the logistics that comprises resin melt after forcing machine leaves at melt.With this kind mode, eliminated the vp that accumulates in the forcing machine, and dispersion-s for example forms in the rotor stator mixing machine at the secondary mixing device.

In interchangeable embodiment; One or more alkyd that will be liquid or fusion form are fed to first mixing device for example in the rotor stator mixing machine; And it is contacted with optional neutralizing agent with water, thereby form the high dispersive phase emulsion in the presence of one or more stablizers.Then, the high dispersive phase emulsion is contacted with other water, thereby prepare alkyd dispersion-s of the present invention.One or more alkyd can be through for example Melt Pump fusion.Such Melt Pump is normally well known by persons skilled in the art.

The glossiness of the film that is formed by the moisture alkyd dispersion-s of the present invention is greater than 75%; For example greater than 80%; Or, for example, greater than 85%.Measure concrete glossiness, for example, on atresia substrate such as Leneta panel 60 ° of measurements.Do not contain any volatile organic compounds on dispersion-based of the moisture alkyd of the present invention; For example, the moisture alkyd dispersion-s of the present invention does not contain any volatile organic compounds.Be substantially free of any volatile organic compounds for example some solvent be meant that alkyd dispersion-s of the present invention comprises any volatile organic compounds that is less than 0.5 weight %, based on the gross weight of dispersion-s; For example, be less than 0.05 weight %, or be less than 0.01 weight %.The viscosity of the moisture alkyd dispersion-s of the present invention is 100 to 10,000cP; For example, be 100 to 1,000cP.The pH of the moisture alkyd dispersion-s of the present invention is less than 12; For example, less than 11, or less than 10, or less than 9, and greater than 5, or greater than 6, or greater than 7.

Preparation according to the present invention is moisture, the continuation method of high solid, solvent-free alkyd dispersion-s may further comprise the steps: (1) provides one or more fusions or liquid alkyd, and wherein said one or more fusions or liquid alkyd acid number separately are less than 20 and molecular weight (M _n) greater than 1000 dalton; (2) one or more stablizers are provided; (3) water is provided; (4) one or more neutralizing agents randomly are provided; (5) in water in the presence of said one or more stablizers and optional said one or more neutralizing agents said one or more fusions of continuous emulsification or liquid alkyd; (6) thus preparation high dispersive phase emulsion; (7) other water is provided; (8) said high dispersive phase emulsion is contacted with said other water; (9) thus prepare said moisture alkyd dispersion-s; Wherein said alkyd dispersion-s comprise 45 to 70 weight % said one or more alkyd, be less than said one or more stablizers of 10 weight %, and the median size of wherein said dispersion-s is 0.05 to 5 μ m.

Alkyd dispersion-s of the present invention can be used for, and for example, different coatings is used like industrial coatings applications, building coats application, automotive coatings application, outdoor furniture coatings applications.

Comprise the dope layer that links to each other with one or more surfaces of goods or structure according to articles coated of the present invention or structure, wherein said dope layer is derived from according to alkyd dispersion-s of the present invention.

Be applicable to that siccative of the present invention includes but not limited to, comprises the compound of metal; For example, the compound that comprises cobalt, zirconium, manganese, calcium, zinc, copper, barium, vanadium, cerium, iron, potassium, strontium, aluminium, bismuth and lithium.The instance of nonmetal siccative promotor comprises oxine, quinoline, salicyl ethylidenehydroxylamine, pyridine-2-formaldehyde oxime, enamine acetylacetonate, 2-2 '-dipyridyl; Quadrol, tn, pyridine, neighbour-vinyl pyridine, neighbour-EL-970, aniline; Ortho-phenylene diamine, neighbour-Tolylamine, alpha-naphthylamine, neighbour-phenanthroline, dipropylamine; Diamyl amine, vinyl cyanide, sym-dicyanoethane, neighbour-toluic nitrile, neighbour-toluamide; The pyrroles, benzoglyoxaline, benzotriazole, UVNUL MS-40, UVNUL MS-40 methacrylic ester etc.The amount of siccative and siccative promotor can based on the gross weight of alkyd, for example, be 0.0002 weight % to 0.5 weight %, based on the weight of alkyd for 0.0002 weight % to 1.0 weight %; Or in interchangeable embodiment, be 0.0005 weight % to 0.5 weight %.Oxi-coating (OMG Fe backbone drying prescription) and the combination of Co Hydro-Cure II, Dri-RX HF and Zr Hydro-CEM can be used to obtain having the coating of improving performance profile.

Alkyd dispersion-s according to the present invention is a film-forming composition.The film that is derived from alkyd dispersion-s of the present invention can have any thickness; For example, the thickness of such film can be 0.01 μ m to 1mm; Or in interchangeable embodiment, be 1 μ m to 500 μ m; Or in interchangeable embodiment, be 1 μ m to 100 μ m; Or in interchangeable embodiment, be 1 to 50 μ m; Or in interchangeable embodiment, be 1 μ m to 25 μ m; Or in interchangeable embodiment, be 1 to 10 μ m.

The method for preparing coated products or structure according to the present invention may further comprise the steps: (1) selects alkyd dispersion-s of the present invention (2) the alkyd dispersion-s to be applied over one or more surfaces of goods or structure; (3) remove a part of water from the alkyd dispersion-s that links to each other with one or more surfaces of goods or structure; (4) thus be coated with said goods or structure.

The present invention includes the coloured coating that is derived from the water base alkyd dispersion-s of the present invention, the anti-wiping of this coating is higher than wipe cycle 300 times, is preferably to be higher than wipe cycle 400 times, more preferably is higher than wipe cycle 500 times.Further provide preparation to have the method that color coating is arranged of good anti-wiping; May further comprise the steps: alkyd dispersion-s of the present invention is selected in (1); (2) formulated of the present invention is become coloured paint vehicle; (3) paint vehicle with said preparation is applied over one or more surfaces or structure, (4) from the alkyd dispersion-s of the said preparation that links to each other with one or more surfaces of goods or structure remove a part of water with (5) thus be coated with said goods or structure; Wherein there is the anti-wiping of color coating to be higher than wipe cycle 300 times, is preferably and is higher than wipe cycle 400 times, be preferably and be higher than wipe cycle 500 times.

The alkyd dispersion-s can be applied over one or more surfaces of goods or structure through any method.Such method includes but not limited to spraying, dipping, roller coat, brushing and those skilled in the art known any other routine techniques usually.Alkyd dispersion-s of the present invention can be applied over one or more surfaces of goods or structure in the temperature that is higher than about 5 ° of C.Such structure includes but not limited to commercial establishment, residential building and warehouse.Alkyd dispersion-s of the present invention can be used as the coating of internal application, applications or its combination.The surface that can be coated with this structure of alkyd dispersion-s of the present invention can comprise concrete, timber, metal, plastics, glass, dry wall etc.

Embodiment

Following examples are explained the present invention but are not limited the scope of the invention.

The embodiment of the invention 1

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 5.4mg KOH, M with Synolac _nBe 3650) be heated to 50 ° of C (to heat approximately 3 to 4 hours to form molten state) and be fed in the rotor-stator mixing machine with 47g/min; Simultaneously; With 25% (w/w) KOH solution with the 1.0g/min charging and with other water blend with the speed pumping of 15g/min, and be injected in the mixing machine to produce the high dispersive phase emulsion.With the mixing machine speed setting at about 780rpm.The median size of the solids content of emulsion is about 1.6 microns.The solids content of high dispersive phase emulsion is 75%, based on the gross weight of dispersion-s.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can be through adding the water dilution with the amount of 25 parts of per 100 parts of initial high dispersive phase emulsions; Thereby form alkyd dispersion-s of the present invention, its solids content is about 60 weight % and viscosity less than 1000cP (through the Brookfield viscometer, axle #2,20rpm, 21 ° of C measure).

The embodiment of the invention 2

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 5.4mg KOH, M with Synolac _nBe 3650) be heated to 50 ° of C (to heat approximately 3 to 4 hours to form molten state) and be fed in the rotor-stator mixing machine with 47g/min.With 25% (w/w) AMP solution with the 1.6g/min charging and with its with the other water of the speed pumping of 10g/min with the other tensio-active agent Triton CF-10 blend of the speed pumping of 2.0g/min, and be injected in the mixing machine to produce emulsion.With the mixing machine speed setting at about 780rpm.The median size of the solids content of emulsion is 0.96 micron.The solids content of high dispersive phase emulsion is 81%.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can be through adding the water dilution with the amount of 35 parts of per 100 parts of initial high dispersive phase emulsions; Thereby form alkyd dispersion-s of the present invention, its solids content is about 60 weight % and viscosity less than 1000cP (through the Brookfield viscometer, axle #2,20rpm, 21 ° of C measure).

The embodiment of the invention 3

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH, M with Synolac _nBe 3650) be heated to 50 ° of C (to heat approximately 3 to 4 hours to form molten state) and with the 15g/min charging and with oleic acid blend with the 0.9g/min charging, and be injected in the rotor-stator mixing machine.25% (w/w) AMP solution with the 2.0g/min charging and with itself and other water blend with the speed pumping of 3g/min, and is injected in the mixing machine to produce the high dispersive phase emulsion.With the mixing machine speed setting at about 1300rpm.The median size of the solids content of emulsion is 0.32 micron.The solids content of high dispersive phase emulsion is 76%.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can be through adding the water dilution with the amount of 27 parts of per 100 parts of initial high dispersive phase emulsions; Thereby form alkyd dispersion-s of the present invention, its solids content is about 60 weight % and viscosity less than 1000cP (through the Brookfield viscometer, axle #2,20rpm, 21 ° of C measure).

The embodiment of the invention 4

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH, M with Synolac _nBe 3650) be heated to 50 ° of C (to heat approximately 3 to 4 hours to form molten state) and be fed in the rotor-stator mixing machine with 15g/min.With 25% (w/w) DMEA solution with the 0.8g/min charging and with its with the other water of the speed pumping of 3.0g/min with other tensio-active agent Tergitol 15-s-30 (70% activeconstituents in the water) blend of the speed pumping of 1.7g/min, and be injected in the mixing machine to produce emulsion.With the mixing machine speed setting at about 1300rpm.The median size of the solids content of emulsion is 0.33 micron.The solids content of high dispersive phase emulsion is 73%.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can be through adding the water dilution with the amount of 22 parts of per 100 parts of initial high dispersive phase emulsions; Thereby form alkyd dispersion-s of the present invention, its solids content is about 60 weight % and viscosity less than 1000cP (through the Brookfield viscometer, axle #2,20rpm, 21 ° of C measure).

The embodiment of the invention 5

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH, M with Synolac _nBe 3650) be heated to 50 ° of C (to heat approximately 3 to 4 hours to form molten state) and be fed in the rotor-stator mixing machine with 15g/min.With 28% (w/w) solution of ammonium hydroxide with the 0.15g/min charging and with the other water of the speed pumping of 2.0g/min with other surfactant R hodapex CO-436 (58% activeconstituents) blend of the speed pumping of 0.5g/min, and be injected in the mixing machine to produce emulsion.With the mixing machine speed setting at about 1300rpm.The median size of the solids content of emulsion is 0.44 micron.The solids content of high dispersive phase emulsion is 85%.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can be through adding the water dilution with the amount of 40 parts of per 100 parts of initial high dispersive phase emulsions; Thereby form alkyd dispersion-s of the present invention, its solids content is that about 59 weight % and viscosity are about 180cP (through the Brookfield viscometer, axle #2,20rpm, 21 ° of C measurements).

The embodiment of the invention 6

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH, M with long oil alkyd resin (long oil alkyd resin) _nBe 3650) be heated to 50 ° of C (to heat approximately 3 to 4 hours to form molten state) and be fed in the rotor-stator mixing machine with 15g/min.With 28% (w/w) solution of ammonium hydroxide with the 0.15g/min charging and with the other water of the speed pumping of 3.5g/min with other surfactant R hodapex CO-436 (58% activeconstituents) blend of the speed pumping of 1.55mL/min, and be injected in the mixing machine to produce the high dispersive phase emulsion.With the mixing machine speed setting at about 1300rpm.The median size of the solids content of emulsion is 0.14 micron.The solids content of high dispersive phase emulsion is 80 weight %.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can be through adding the water dilution with the amount of 14 parts of per 100 parts of initial high dispersive phase emulsions; Thereby form alkyd dispersion-s of the present invention, its solids content is that 70 weight % and viscosity are about 47000cP (through the Brookfield viscometer, axle #7,20rpm, 21 ° of C measurements).Dispersion-s of the present invention is through the water dilution of the amount of 40 parts of per 100 part of 70 weight % solids contents of interpolation.The solids content of the dispersion-s of the present invention of dilution is that 48 weight % and viscosity are about 90cP (through the Brookfield viscometer, axle #1,20rpm, 21 ° of C measurements).The hot ageing stability of dispersion-s of the present invention was at least 12 weeks, and wherein final size is 0.19 micron, solids content aspect no change.

The embodiment of the invention 7

Medium oil alkyd resin (the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH) is heated to 80 ° of C (to heat approximately 3 to 4 hours to form molten state) and is fed in the rotor-stator mixing machine with 15g/min.With 28% (w/w) solution of ammonium hydroxide with the 0.15g/min charging and with the other water of the speed pumping of 2.9g/min with other surfactant R hodapex CO-436 (58% activeconstituents) blend of the speed pumping of 1.55mL/min, and be injected in the mixing machine to produce the high dispersive phase emulsion.With the mixing machine speed setting at about 1300rpm.The median size of the solids content of emulsion is 0.18 micron.The solids content of high dispersive phase emulsion is 81 weight %.The viscosity of this high dispersive phase emulsion 100,000cP.The high dispersive phase emulsion can dilute through adding water to initial high dispersive phase emulsion with the speed of 12g/min subsequently; Thereby form alkyd dispersion-s of the present invention, its solids content is that about 50 weight % and viscosity are about 200cP (through the Brookfield viscometer, axle #7,20rpm, 21 ° of C measurements).The hot ageing stability of dispersion-s of the present invention was at least 12 weeks, and wherein final size is 0.18 micron, solids content aspect no change.

The embodiment of the invention 8

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH, M with Synolac _nBe 3650) with AMP-95 be distributed in the rotor stator mixing machine with in 95% acid groups, dispersions obtained pH is 8.9, median size is 2.5 microns, polymolecularity be 0.78 with solids content be 62%.

The standard siccative bag that comprises 0.5 weight %Cobalt Hydrocure, 0.1 weight %DryRx HF and 1.1 weight %Zirconium Hydro is added in the dispersion-s; Prepare a series of mixtures; Wherein (a) surfactant-free or solvent; (b) 1 weight % tensio-active agent (Tergitol 15-S-3), (c) 1.5 weight % solvents (diethylene glycol monobutyl ether).Extremely about 9 repeat a series of experiments through pH before adding siccative, tensio-active agent or solvent with AMP-95 adjusting dispersion-s.

Make on the film on dispersion-s dirty (draw down) to the Leneta paper, confirm Ranvier's membrane character, shown in Table I.The result shows, dispersion-s of the present invention even use non-optimized preparation to make good film.

Table I

The embodiment of the invention 9

(the solvent-free form of Deltech 300-70M, acid number are the every gram resin of 9.0mg KOH, M with Synolac to use sulfation alkylphenol ethoxylate tensio-active agent (Rhodapex CO-436) at three kinds of surfactant content (0%, 2%, 6%) _nBe 3650) with ammonia be distributed in the rotor stator mixing machine with in 95% acid groups.The solids content of gained high dispersive phase solution is 70%, and its median size is respectively 4 microns, 0.45 micron and 0.16 micron.The experiment of another high dispersive phase emulsion is carried out in 70% solids content, and wherein using in the ammonia and obtaining median size with 95% acid groups with the reactive surfactant (ammonium oleate) that uses 6% is 0.36 micron.

Four kinds of high solids dispersive alkyd water or acetone diluted in water; Reaching solids content is 40 weight %, and adds in the dispersion-s standard siccative bag that comprises 0.5 weight %Cobalt Hydrocure, 0.1 weight %DryRx HF and 1.1 weight %Zirconium Hydro and thorough mixing.Confirm the barrier of anti-tannin the (tannin block resistance) of coating, compare with commercial WB alkyd paint vehicle of preparing and SB alkyd paint vehicle with this result and with the commercial WB alkyd dispersion-s that the starting point preparation of manufacturer is prepared.The tannin of dispersion-s of the present invention pollutes the result who intercepts test and is reported in Table II.The result of suitable WB and SB alkyd is reported in Table III, IV and V.

Table II

The anti-tannin contaminative of the embodiment of the invention

Relatively at the same solid content of 40 weight %, 27 weight %) and water-reducible (water-content: the result of dispersion-s 60 weight %) shows that the water of minimizing system helps to improve anti-tannin contaminative the (water-content: of acetone diluted.SB alkyd is widely used as and can surfaces coated be furnished with any latex or alkyd capital construction and builds the height of the inside and outside purposes of paint vehicle and cover to pollute and intercept primer.It is the basic function that primer is used that good pollution intercepts, and with the acrylic emulsions compared with techniques of oozing out that is used to intercept trees tannin and resin, alkyd provides preferable performance.Good trees pollute that to intercept be key request, and WB alkyd has potential to substitute building and industrial maintenance (AIM) coating, condition be their tannin pollution barrier property greater than 93%, be preferably more than 95% or more more preferably greater than 98%.

Table III

The commercial not anti-tannin contaminative of the WB alkyd dispersion-s of preparation

Table IV

The anti-tannin contaminative of the WB alkyd dispersion-s of commercial preparation

Table V

The anti-tannin contaminative of the SB alkyd of commercial preparation

Above result shows; Made by the high solid WB alkyd dispersion-s of the present invention (having low acid number, solvent-free Synolac and low surfactant and amine content) of rotor stator method preparation and to have unexpected enhanced propertied coating, the anti-tannin that for example improves pollutes barrier.Such WB alkyd can solve this market unsatisfied demand of low VOC substitute of SB alkyd in the AIM coatings applications with good anti-tannin pollution barrier.

The embodiment of the invention 10

Deriving from the embodiment of the invention 8 is 40 weight % at the alkyd high dispersive phase emulsion of 70 weight % solids contents (use in the ammonia with 95% acid groups and obtain 0.36 micron median size with the reactive surfactant (ammonium oleate) that uses 6 weight %) water or acetone diluted to solids content, adds in the dispersion-s standard siccative bag that comprises 0.5 weight %Cobalt Hydrocure, 0.1 weight %DryRx HF and 1.1 weight %Zirconium Hydro and thorough mixing.Confirm the grain raising character of coating and be reported in Table VI.

Table VI

Relatively at the same solid content of 40 weight %, 27 weight %) and water-reducible (water-content: the result of dispersion-s 60 weight %) shows that the water of minimizing system helps to reduce the grain raising of timber substrate the (water-content: of acetone diluted.When using water-based paint, grain raising is owing to water absorption gets into the problem that causes in the fiber, and this makes that loose and feasible wood grain (wood grain) on every side keeps clear to filamentary fibers (stringy fibers) in the surface.This problem uses rumbling compound based on water through the preliminary wetting wood grain with after using fine sand sander (fine grit sander) drying, polish off fine, soft fur and be able to alleviate, this.Less grain raising is required, because this make to reduce the needs of fine sand polishing between coating and reduces application cost and the parts of coating are back to the time that makes use.

Above result shows that the high solid WB alkyd dispersion-s of the present invention (having low acid number, Synolac and low surfactant and amine content) that is prepared by the rotor stator method makes the coating with unexpected enhanced propertied (grain raising that for example reduces).Such WB alkyd can solve low this market unsatisfied demand of VOC WB substitute of SB alkyd in having the AIM coatings applications that reduces application cost.

The embodiment of the invention 11 and 12: through the alcoholysis-esterification synthetic alkyd resin of oil

Fs

The synthetic schemes that is used to prepare Synolac is two stage alcoholysis-polyesterification method.In the fs, carry out typical alcoholysis reaction in enormous quantities, product is divided into quarter is used for next step.In three mouthfuls of RB flasks of 5L, add sunflower oil.Intermediate head place that glass agitator arm and oar are placed flask.Flask is connected in the bracing frame with unsettled stirring, and the oil bath that will be in room temperature is raised with the submergence flask.Oil bath is set at 220 ° of C and begins heating and stirring.In the sunflower oil that stirs, add TriMethylolPropane(TMP) (TMP), tetramethylolmethane (PE) and dibutyl tin oxide (DBTO) (1200ppm is based on amount of fill).After having added all reactants, be that the filling type condensing surface of 95 ° of C is connected in binding with the flexible pipe bifurcated interface (hosebarb adaptor) that is connected in bubbler in the lump of side connector with a setting point.The opposite side eck is connected with flexible pipe bifurcated interface and is connected in nitrogen inlet.In system, slowly be blown into nitrogen and observe bubbler.Make reaction mixture heating and mixed 16 hours, normally heat and mixes and spend the night to guarantee to form monoglyceride, this verifies through the solvability in 4 parts of methyl alcohol.Second day, flask is shifted out oil bath, the 900g equal portions are transferred in three mouthfuls of RB flasks of independent 2L.Make flask at N ₂Protection cooling is down used until preparation.

Table VII

The embodiment of the invention	Composition →	TMP	PE	Oil	M-phthalic acid	Tetra hydro Phthalic anhydride
							11	Base-material 3LO-64	5.977	8.966	61.754	9.321	13.982
12	Base-material 7MO-56	7.813	11.720	53.645	10.729	16.093

Subordinate phase

The 2L round-bottomed flask (RBF) that comprises the alcoholysis mixture is equipped with glass agitator arm and oar.Flask is connected in bracing frame with unsettled stirring.The oil bath that will be in room temperature is raised with the submergence flask.Oil bath is set at 220 ° of C and begins heating and stirring.In flask, add m-phthalic acid (PIA), Tetra hydro Phthalic anhydride (PAN) and the YLENE (2%) of purifying based on total amount of fill.Then, the Dean-Stark water trap is connected in binding with the Friedrichs condensing surface that is connected in bubbler in the lump of side connector.The flexible pipe bifurcated interface that is connected in nitrogen inlet is connected with the opposite side joint.In system, be blown into nitrogen.Distill out the water of formation with system heating (~ 220 ° of C) and with form with the azeotropic mixture of YLENE.After 3 hours, collect 1 ~ 2g reaction mixture and titration to confirm acid number (AV).Reaction is carried out until reaching required AV, and AV is 8-10 in this case, then reaction content is poured in the glass jar, makes it under nitrogen protection, be cooled to room temperature.The embodiment of the invention 11 and 12 viscosity in the shearing rate of 80 ° of C and 0.10/sec are respectively 1107 and 26600 centipoises (mPas).

The embodiment of the invention 13

The Synolac that derives from the embodiment of the invention 12 is heated to 60 ° of C (to heat approximately 3 to 4 hours to form molten state) and is fed in the rotor-stator mixing machine with 15g/min.With 28% (w/w) solution of ammonium hydroxide with the 0.077g/min charging and with the other water of the speed pumping of 2.0g/min with other tensio-active agent E-sperse 100 (60% activeconstituents) blend of the speed pumping of 1.0mL/min, and be injected in the mixing machine to produce the high dispersive phase emulsion.The mixing machine speed setting is at about 1300rpm.The median size of the solids content of emulsion is 0.18 micron.The solids content of high dispersive phase emulsion is 86 weight %.The high dispersive phase emulsion dilutes through adding water to initial high dispersive phase emulsion with 11g/min after a while; Thereby form alkyd dispersion-s 13 of the present invention, its solids content is 52 weight %, and viscosity is about 700cP (through the Brookfield viscometer, axle #7,20rpm, 21 ° of C measurements).The hot ageing stability of dispersion-s of the present invention was at least 12 weeks, and wherein final size is 0.19 micron, solids content aspect no change.

The embodiment of the invention 14

Alkyd dispersion-s 13 of the present invention is mixed with coating composition A.Formulation component is reported in Table VIII.With component 1-4 in container pre-mixing to form premix 1.With component 5-9 in grinding pot (grind pot) pre-mixing to form premix 2.Add premix 1 in the grinding pot premix 2; Thereby form premix 3.Premix 3 mixes and adds component 10 to premix 3 by part and mixed about 25 minutes with 2500rpm simultaneously through the high speed dispersion device; Thereby form premix 4.With component 11-13 pre-mixing to form premix 5 through desk-top mixing machine.Premix 4 added in the premix 5 simultaneously mix with formation premix 6 with about 900rpm.Component 14-17 premix is incorporated in the sealed vessel through physical vibration formation premix 7.Premix 7 added to continue simultaneously in the premix 6 to mix to form final coating composition A with about 900rpm.Through by part add component 18-20 with the viscosity adjustment of the final coating composition A imperial chemical industry value (imperial chemical industry) to about 2 (ICI) with about krebs units of 95 to 100 (krebs unit) (KU).Measure the anti-wiping of final coating composition B, the result is reported in Table VIII.

Table VIII

Component	Title material	Poundage
			1	Water	41.78
2	Natrosol?Plus?330	0.38
			3	Bentone?EW	0.42
4	AMP-95	0.32
			5	Disperbyk?190	1.26
6	Triton?CF-10	0.38
			7	Water	15.31
8	Rhodoline?643	0.26
			9	Acrysol?EM-8W	1.51
10	Ti-Pure?R-706	141.29
			11	AF29-R1	273.20
12	Water	24.17
			13	BYK-011	0.50
14	Cobalt?Hydro-Cure?II?w?VOC	1.50
			15	Dri-RX?HF?w?VOC	0.38
16	Zirconium?Hydro?CEM?w?VOC	3.14
			17	Ucar 35	3.92
18	Water	7.00
			19	Acrysol?RM-8W	0.00
20	Acrysol?RM-2020NPR	19.00

The embodiment of the invention 15

Synolac base-material 7 is heated to 60 ° of C (to heat approximately 3 to 4 hours to form molten state) and is fed in the rotor-stator mixing machine with 15g/min.With 28% (w/w) solution of ammonium hydroxide with the 0.077g/min charging and with the other water of the speed pumping of 2.0g/min with other tensio-active agent E-sperse 100 (60% activeconstituents) blend of the speed pumping of 0.5mL/min, and be injected in the mixing machine to produce the high dispersive phase emulsion.The mixing machine speed setting is at about 1300rpm.The median size of the solids content of emulsion is 0.46 micron.The solids content of high dispersive phase emulsion is 87 weight %.The high dispersive phase emulsion dilutes through adding water to initial high dispersive phase emulsion with 11g/min after a while; Thereby form alkyd dispersion-s of the present invention, its solids content is 53 weight %, and viscosity is about 300cP (through the Brookfield viscometer, axle #7,20rpm, 21 ° of C measurements).The hot ageing stability of dispersion-s of the present invention was at least 12 weeks, and wherein final size is 0.46 micron, solids content aspect no change.

The embodiment of the invention 16

Synolac base-material 3 is heated to 35 ° of C (to heat approximately 3 to 4 hours to form molten state) and is fed in the rotor-stator mixing machine with 15g/min.With 28% (w/w) solution of ammonium hydroxide with the 0.11g/min charging and with the other water of the speed pumping of 2.0g/min with other tensio-active agent E-sperse 100 (60% activeconstituents) blend of the speed pumping of 1.0mL/min, and be injected in the mixing machine to produce the high dispersive phase emulsion.The mixing machine speed setting is at about 1300rpm.The median size of the solids content of emulsion is 0.43 micron.The solids content of high dispersive phase emulsion is 86 weight %.The high dispersive phase emulsion dilutes through adding water to initial high dispersive phase emulsion with 11g/min after a while; Thereby form alkyd dispersion-s of the present invention, its solids content is 52 weight %, and viscosity is about 850cP (through the Brookfield viscometer, axle #7,20rpm, 21 ° of C measurements).

The embodiment of the invention 17

Alkyd dispersion-s 16 of the present invention is mixed with coating composition B.Formulation component is reported in Table I X.With component 1-4 in container pre-mixing to form premix 1.With component 5-9 in grinding pot pre-mixing to form premix 2.Add premix 1 in the grinding pot premix 2; Thereby form premix 3.Premix 3 mixes and adds component 10 to premix 3 by part and mixed about 25 minutes with 2500rpm simultaneously through the high speed dispersion device; Thereby form premix 4.With component 11-13 pre-mixing to form premix 5 through desk-top mixing machine.Premix 4 added in the premix 5 simultaneously mix with formation premix 6 with about 900rpm.Component 14-17 premix is incorporated in the sealed vessel through physical vibration formation premix 7.Premix 7 added to continue simultaneously in the premix 6 to mix to form final coating composition A with about 900rpm.Through by part adding component 18-20 with the viscosity adjustment of final coating composition A imperial chemical industry value (ICI) and about 95 to 100 the krebs units (KU) to about 2.Measure the anti-wiping of final coating composition B, the result is reported in Table I X.

Table I X

Component	Title material	Poundage
			1	Water	41.78
2	Natrosol?Plus?330	0.38
			3	Bentone?EW	0.42
4	AMP-95	0.32
			5	Disperbyk?190	1.26
6	Triton?CF-10	0.38
			7	Water	15.31
8	Rhodoline?643	0.26
			9	Acrysol?EM-8W	1.51
10	Ti-Pure?R-706	141.29
			11	AG01-R1	264.05
12	Water	28.78
			13	BYK-011	0.50
14	Cobalt?Hydro-Cure?II?w?VOC	1.50
			15	Dri-RX?HF?w?VOC	0.38
16	Zirconium?Hydro?CEM?w?VOC	3.14
			17	Ucar 35	3.92
18	Water	3.12
			19	Acrysol?RM-8W	0.00
20	Acrysol?RM-2020NPR	22.88

Table X shows that the high solid WB alkyd dispersion-s of the present invention (having low acid number, solvent-free Synolac and low surfactant and amine content) that is prepared by the rotor stator method makes the coating with unexpected anti-wiping of enhancing.

Table X

Testing method

Testing method comprises following:

Acid number is confirmed

Use glass pipet that 1 ~ 2g sample of alkyd is shifted out and weighs and put into the 250mLErlenmeyer flask from reactor drum.50/50 Virahol/xylene mixture of 25mL is added in the flask, use stirring rod simultaneously.Flask is placed on the stirrer/hot plate and under mild heat, it is mixed until substance dissolves.Then, several phenolphthalein indicator solution are added in the flask and use 0.1N Pottasium Hydroxide in methyl alcohol with the flask contents titration to phenolphthalein terminal point.Then according to computes AV:

The unlimited time is meant that the dispersion-s of preparation keeps enough moistening or unlimited (open) time spans to allow brush to go into (brush-in) and repair.There is not the ASTM test of confirming the time of opening wide.

The time of opening wide is confirmed through following steps: uniform film of curtain coating and the defective that on coating, makes a mark and brush out above that at interval at different time with simulation on the Leneta of 8X11 inch panel.Confirm to remove through brushing the effectiveness of original tally, the time of opening wide is corresponding to until still can remove the time of mark.

Grain raising is the problem that water-based paint has, and is owing to by due to the absorption of the cell wall fragment on the wood surface water, cause the surface fiber (carefully palpus) of timber to erect from wood surface, produces rough grain.There is not the ASTM testing method of identifying the grain raising severity.

Grain raising is gone up to southern yellow pine (Southern Yellow Pine) through applying coating and is confirmed that said southern yellow pine is the timber with inhomogeneous wood grain, has significant burr and unique annual ring, comprises that the light and soft layer of spring wood is the heavy blindstory of summerwood then.Compare with summerwood,, cause lower glossiness reading, show that grain raising increases because higher porousness dispersion-s is penetrated into spring wood more.Grain raising is being confirmed through vision and sense of touch grade qualitatively, is quantitatively measured by glossiness and confirms.

Anti-tannin pollutes barrier and measures the ability that other natural timber pollution of coating obstruct water-soluble mono peace is exuded to top coat.Use the invulnerable release of ASTM D6686, promptly be used to estimate the testing method of the anti-tannin contaminative of coating.

The tannin obstruct is tested the white primer lacquer that comprises by the alkyd formulated and is coated on Chinese larch or the western Western Red Cedar (western red cedar) (timber with high tannin content); Solidified 24 hours, with white outside paint vehicle surface coated with solidified once more 24 hours.Y reflectivity is confirmed through BYK Gardner color observation spectrophotometer.The concentrated tstr (condensation tester) of high humidity Cleveland that plate is put at 100 ° of F reaches 96 hours; Cooling and dry; Refetch reading in same position, confirm primer and top coat finally with the ratio of original reflection rate (because the tannin of coating decolouring is oozed out).

Anti-wiping testing method

This test (based on ASTM D 2486-00) is carried out as follows:

A. instrument is prepared:

Wear testing device-use wear testing device, it comprises the brush that is clipped on the support, this brush can apply at exsiccant through one group of cable at either side on the film of paint vehicle and move around.Make wear testing device maintenance level before use and with the operation of 37 ± 1 cycles per minute.

Brush-if new, make bristle maintenance level before use is to allow evenly friction on the paint vehicle surface.The maintenance level is accomplished through making brush go up to move at the intensive sand grains sand paper of 100 or 120 order aluminum oxide (close grain sandpaper).

B. test:

7 mil perforates of coating use 7/10Dow film curtain coating device begin drawing-off (drawn down) to black vinyl figure (vinyl chart) (type P-121-10N, The Leneta Company) from the safe end of panel.To apply the time be 3 to 4 seconds from end-to-end.Coating in the unlimited room that keeps 73.5+/-3.5 ° F. and 50+/-5% relative humidity air-dry 7 days at level attitude.Each sample is carried out twice drawing-off.Each drawing-off thing is cut in half, whole four are tested.Framework through using the liner assembling and brass counterweight or anchor clamps are fixed on the drawing-off thing in the wear testing device.Brush is rack-mount.(wearing and tearing wiping media, type SC-2, The 15 Leneta Company) are laid on the brush bristle equably with the 10g wiping media.Brush is placed the center in path.When using wiping media and water, edge-on of the bristle of brush, then when beginning to test carefully with turning up under the bristle side direction.After per 400 circulations before failure, remove brush but do not wash brush; Add the wiping media that 10g stirs; Replace brush.Before continuing, 20ml water is placed on the brush.Be recorded in and remove the required number of cycles of paint vehicle film in the continuous route fully.

The glossiness surface measurements is at the reflectivity of specific reflection angle.Coating gloss uses BYK Gardner multi-angle glossmeter to confirm at 20 and 60 degree according to ASTM D523.

Median size can be used particle size analyzer or use transmission electron microscopy (TEM) or scanning electron microscopy (SEM) to measure through electron microscope method through light scattering method.

Particle size analyzer

Beckman Coulter LS230 particle size analyzer uses with the small footprint modular (Small Volume Module) as sample delivery system.The software version that uses is Version 3.29.Hardware and software is available from Beckman Coulter Inc., Miami, Florida.

All Analysis of measuring conditions are used 1.332 fluid refracting rate, 1.5 sample actual refractive index and 0.0 sample supposition specific refractory power.Do not use the optical model of expansion.Activate polarization intensity differential scattering (PIDS) option, and be used to produce granular information.Measure median size, and report with μ m.

Electron microscope method

(1)TEM

At first with sample with distilled water diluting (1 latex is in the 10mL deionized water), then ~ 5 μ L drops are placed on the TEM grid of Formvar (polyvinyl form) coating, make it air-dry.Sample uses at the JEOL JEM-1230TEM of the acceleration voltage operation of 120kV and uses standard samples frame or use to check in the freezing stage of-120 ° of C (cryo-stage).Digital picture uses resolving power to obtain and use Adobe Photoshop 5.0 processing as the Gatan Multiscan 794 CCD photographic cameras of 1024x1024 pixel.Image analysis uses ImageJ software to carry out.(threashold) is applied to the grey scale image with threshold value, uses watershed divide function (watershed function) to separate aggregate, measures the particle area.Through equation diameter=2*sqrt (area/π) the particle area is converted into diameter of equal value.Diameter range is ~ particle of 3nm to 3 μ m can pass through the TEM commercial measurement.

(2)SEM

Sample is diluted with deionized water, then it is dropped on the fragment of clean silicon wafer and in drying at room temperature.After with 10nm osmium sputter coating, they are formed images 3 to 5keV in the pistol sem of FEI Nova NanoSEM field.Image analysis uses ImageJ software to carry out.Threshold value is applied to the grey scale image, uses the watershed divide function to separate aggregate, measure the particle area.Through equation diameter=2*sqrt (area/π) area is converted into diameter.Diameter that can measurement of ~ 50nm to 50 μ m.

The viscosity of alkyd dispersion-s in water can be measured at 20rpm and 21 ° of C through the Brookfield viscometer.

The solids content of hot ageing stability through remeasuring (after the circulation of assigned temperature and time) granularity and dispersion-s is definite to determine whether to change.Dispersion samples is placed in the glass jar of band plastic cover.Glass jar is placed in the baking oven of the temperature that is set in 50 ° of C and makes it be placed to many 12 weeks.When this finishes time period, if do not observe the sedimentation/separation of dispersion-s with eye, so according to before the process of description remeasure the granularity of sample.

The viscosity of Synolac in melt

The viscosity measurement of alkyd uses TA Instruments AR 2000 rheometers to carry out.The sample of alkyd is measured through the rheometer (flow rheometry) that flows and is used the parallel plate geometry body in the assigned temperature analysis.Viscosity is by the torque arithmetic of measuring and based on the special-purpose factor and to measure shearing rate be 0.10/sec of rectifying an instrument of test solid.

The present invention can not deviate from its spirit and the basis of essential attribute with other form enforcement, therefore, when indicating the scope of the invention, should be with reference to accompanying claims, but not aforementioned specification.

Claims

1. moisture, high solid, solvent-free alkyd dispersion-s comprise:

One or more alkyd of 40 to 70 weight %, based on the gross weight of said dispersion-s, wherein said one or more alkyd acid number separately is less than 20 and molecular weight (M _n) greater than 1000 dalton;

One or more tensio-active agents that are less than 10 weight % are based on the gross weight of said dispersion-s; With

The water of 30 to 55 weight % is based on the gross weight of said dispersion-s;

The median size of wherein said dispersion-s is 0.05 to 5 μ m.

2. according to the moisture alkyd dispersion-s of claim 1, wherein said one or more alkyd are neutralized to many 100% by neutralizing agent.

3. according to the moisture alkyd dispersion-s of claim 1, the viscosity of wherein said dispersion-s is 100 to 10,000cP.

4. according to the moisture alkyd dispersion-s of claim 1, wherein said one or more alkyd are neutralized to many 200% by neutralizing agent.

5. prepare the solvent-free continuation method of moisture alkyd dispersion-s, may further comprise the steps:

One or more fusions or liquid alkyd are provided, wherein said one or more fusions or liquid alkyd acid number separately less than 20 and molecular weight (Mn) greater than 1000 dalton;

One or more tensio-active agents are provided;

Water is provided;

One or more neutralizing agents randomly are provided;

In water in the presence of said one or more tensio-active agents and optional said one or more neutralizing agents said one or more fusions of continuous emulsification or liquid alkyd;

Thereby preparation high dispersive phase emulsion;

Other water is provided;

Said high dispersive phase emulsion is contacted with said other water;

Thereby prepare said moisture alkyd dispersion-s; Wherein said alkyd dispersion-s comprise 40 to 70 weight % said one or more alkyd, be less than said one or more tensio-active agents of 10 weight %, and the median size of wherein said dispersion-s is 0.05 to 5 μ m.

6. according to the continuation method of the moisture alkyd dispersion-s of the preparation of claim 5, wherein said one or more alkyd are neutralized to many 100% by neutralizing agent.

7. according to the continuation method of the moisture alkyd dispersion-s of the preparation of claim 5, the viscosity of wherein said dispersion-s is 100 to 10,000cP.

8. according to the continuation method of the moisture alkyd dispersion-s of the preparation of claim 5, wherein said one or more alkyd are neutralized to many 200% by neutralizing agent.

9. the coating composition that comprises the dispersion-s of claim 1.

10. be derived from the coating layer of the coating composition of claim 9.

11. each in the aforementioned claim, the solids content of wherein moisture alkyd dispersion-s are greater than 60wt%, based on the weight of said dispersion-s.

12. each in the aforementioned claim, the solids content of wherein moisture alkyd dispersion-s are greater than 65wt%, based on the weight of said dispersion-s.

13. each in the aforementioned claim, the solids content of wherein moisture alkyd dispersion-s are greater than 70wt%, based on the weight of said dispersion-s.

14. each in the aforementioned claim, the acid number of wherein said Synolac is less than 20.

15. each in the aforementioned claim, the acid number of wherein said Synolac is less than 15.

16. each in the aforementioned claim, the acid number of wherein said Synolac is less than 10.

17. preparation has the method for coating of good anti-wiping, may further comprise the steps: (1) is selected according to each alkyd dispersion-s in the aforementioned claim, and (2) become coloured paint vehicle with said alkyd formulated, (3) thus form the paint vehicle of preparation; (4) paint vehicle with said preparation is applied over one or more surfaces or structure, (5) from the paint vehicle of the said preparation that links to each other with one or more surfaces of goods or structure, remove a part of water with (5) thus be coated with said goods or structure.